Electric field-driven folding of single molecules

Abstract

Folding of molecules is an essential process in nature, and various molecular machines achieve their chemical and mechanical function via controlled folding of molecular conformations. The electric field offers a unique strategy to drive the folding of molecular conformation and to control charge transport through single molecules but remains unexplored. The single-molecule break junction technique provides access to detect the conformational changes via the monitoring of single-molecule conductance, and the electric field between two metal electrodes with nanoscale spacing can provide an extremely strong to achieve in-situ control and detection of molecular folding at the single-molecule level. Here, we use the electric field to control the single-molecule folding using the scanning tunneling microscope break junction (STM-BJ) technique. The electric fields induced folding could lead to a ∼1400% conductance change of the single-molecule junctions, and the folding/unfolding process can be in-situ switched at the scale of milliseconds. DFT calculations suggest the conformational control originates from the electric field-induced charge injection, and the formation of homoconjugated conformation with the overlapped orbitals. This work provides the first demonstration of electric field-driven molecular folding, which is essential for the understanding of molecular machines in nature and for the design of artificial molecular machines.